Compatibility,crystallinity and mechanical properties of poly(lactic acid)‐poly(ether‐block‐amide) based copper nanocomposites

Binary and ternary composites of poly(lactic acid) (PLA), poly(ether‐block‐amide) (PEBAX) and copper nanoparticles were prepared by melt blending in an internal mixer. Compatibility and molecular interactions between the three components of the nanocomposites were evaluated using scanning electron microscopy and Fourier transform infrared spectroscopy. It was found that the carbonyl groups of the PLA and copper nanoparticles interact. Also, PLA and PEBAX are compatible and develop molecular interactions between the C=O of PLA and the C=O and NH of PEBAX, forming dipole–dipole bonds and hydrogen bonds. The compatibility and molecular interaction between PLA and PEBAX are reduced by copper nanoparticles. The reduction of compatibility between PLA and PEBAX produced a lower storage modulus and lower strain at break in the ternary systems than in the blend PLA‐PEBAX. Copper nanoparticles enhanced the crystallinity of PLA. PLA responded more strongly to the nucleating effect of copper when PEBAX was added indicating a synergistic effect. The strain at break of PLA was enhanced by the addition of PEBAX but was severely reduced by the presence of nanoparticles. © 2020 Society of Chemical Industry     

Preparation and properties of poly(ether‐ester‐amide)/poly(acrylonitrile‐co‐butadiene‐co‐styrene) antistatic blends

A novel antistatic agent poly(ether‐ester‐amide) (PEEA) based on caprolactam, polyethylene glycol, and 6‐aminocaproic acid was successfully synthesized by melting polycondensation. The structure, thermal properties, and antistatic ability of the copolymer were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analyses, and ZC36 megohmmeter. Test results show that PEEA is a block copolymer with a melting point of 217°C and a thermal decomposition temperature of 409°C, together with a surface resistivity of 10⁸ Ω/sq. Antistatic poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS) materials were prepared by blending different content of PEEA to ABS resin. The antistatic performances, morphology, and mechanical properties were investigated. It is indicated that the surface resistivity of PEEA/ABS blends decrease with the increasing PEEA content, and the excellent antistatic performance is obtained when the antistatic agent is up to 10–15%. The antistatic performance is hardly influenced by water‐washing and relative humidity, and a permanent antistatic performance is available. The antistatic mechanism is investigated. The compatibility of the blends was studied by scanning electron microscopy images. The ladder distribution of antistatic agent is formed, and a rich phase of antistatic agent can be found in the surface layer. The elongations at break of the blend are improved with the increasing antistatic agent; the tensile strength and the notched impact strength kept almost the same. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Synthesis and properties of copolymers of poly(ether ketone ketone) and poly(ether amide ether amide ether ketone ketone)

Poly(aryl ether ketone)s (PAEKs) are a class of high‐performance engineering thermoplastics known for their excellent combination of chemical, physical and mechanical properties, and the synthesis of semicrystalline PAEKs with increased glass transition temperatures (T_g) is of much interest. In the work reported, a series of novel copolymers of poly(ether ketone ketone) (PEKK) and poly(ether amide ether amide ether ketone ketone) were synthesized by electrophilic solution polycondensation of terephthaloyl chloride with a mixture of diphenyl ether and N,N′‐bis(4‐phenoxybenzoyl)‐4,4′‐diaminodiphenyl ether (BPBDAE) under mild conditions. The copolymers obtained were characterized using various physicochemical techniques. The copolymers with 10–35 mol% BPBDAE are semicrystalline and have markedly increased T_g over commercially available poly(ether ether ketone) and PEKK due to the incorporation of amide linkages in the main chain. The copolymers with 30–35 mol% BPBDAE not only have high T_g of 178–186 °C, but also moderate melting temperatures of 335–339 °C, having good potential for melt processing. The copolymers with 30–35 mol% BPBDAE have tensile strengths of 102.4–103.8 MPa, Young's moduli of 2.33–2.45 GPa and elongations at break of 11.7–13.2%, and exhibit high thermal stability and good resistance to organic solvents. Copyright © 2010 Society of Chemical Industry     

Synthesis of biodegradable amino‐acid‐based poly(ester amide)s and poly(ether ester amide)s with pendant functional groups

A new family of biodegradable amino‐acid‐based poly(ester amide)s (AA–PEAs) and amino‐acid‐based poly(ether ester amide)s (AA–PEEAs) consisting of reactive pendant functional groups (? COOH or ? NH₂) were synthesized from unsaturated AA–PEAs and AA–PEEAs via a thiol–ene reaction in the presence of a radical initiator (2,2′‐azobisisobutyronitrile). The synthetic method was a one‐step reaction with near 100% yields under mild reaction conditions. The resulting functional AA–PEA and AA–PEEA polymers were characterized by Fourier transform infrared spectroscopy, NMR, and differential scanning calorimetry. These new functional AA–PEA and AA–PEEA derivatives had lower glass‐transition temperatures than the original unsaturated AA–PEA and AA–PEEA polymers, and their solubility in some organic solvents also improved. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of new thermally stable poly(ether imide amide)s

2,6‐Bis(4‐aminophenoxy)pyridine was prepared via reaction of 4‐aminophenol with 2,6‐dichloropyridine in the presence of potassium carbonate. Reaction of the diamine with two mol of trimellitic anhydride afforded a diacid with preformed imide structures. Poly(ether imide amide)s were prepared by polycondensation reactions of the diacid with different diamines in the presence of triphenyl phosphite. All the monomers and polymers were fully characterized and the physical properties of the polymers including solution viscosity, thermal stability, thermal behavior and solubility were studied. Thermal analysis data showed the polymers to have high thermal stability. Copyright © 2004 Society of Chemical Industry     

Radiopaque,barium sulfate‐filled biomedical compounds of a poly(ether‐block‐amide) copolymer

Various radiopaque compounds of a poly (ether‐block‐amide) copolymer resin filled with fine barium sulfate particles were prepared by melt mixing. Material properties of the filled compounds were investigated using various material characterization techniques, including thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic rheometry, uniaxial tensile test, and dynamic mechanical thermal analysis (DMTA). The effects of the filler and its concentration on the measured material properties are evaluated. It has been found that in addition to its well‐known X‐ray radiopacity, the filler is quite effective in reinforcing some mechanical properties of the copolymer, including modulus of elasticity and yield strength. More interestingly, it has been observed that at low loading concentrations near 10 wt %, the filler may also act as a rigid, inorganic toughener for the copolymer by improving the postyield material extensibility of strain hardening against ultimate material fracture. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(ether amide)s from p‐xylylene glycol and bis(ether nitrile)s

BACKGROUND: Poly(ether amide)s have been well studied in terms of improving the physical and thermal properties of aromatic polyamides. Poly(ether amide)s of high enough molecular weight to be useful for industrial purposes are generally difficult to prepare. The objective of this project was to introduce a simple and commercially feasible process to prepare poly(ether amide)s by a polymerization reaction at relatively low temperature. RESULTS: A series of poly(ether amide)s were prepared by direct polyamidation of p‐xylylene glycol with bis(ether nitrile)s via the Ritter reaction using concentrated H₂SO₄ in acetic acid. The synthesized poly(ether amide)s showed good solubility in polar aprotic solvents. The resultant poly(ether amide)s had inherent viscosities in the range 0.36–1.03 dL g^?1. The glass transition temperatures of the poly(ether amide)s were determined using differential scanning calorimetry to be in the range 190–258 °C. Thermogravimetric analysis data for these polymers indicated the 10% weight loss temperatures to be in the range 290–390 °C in nitrogen atmosphere. CONCLUSION: The Ritter reaction was applied for the synthesis of a variety of poly(ether amide)s with moderate to high molecular weights. This procedure provides a simple polymerization process for the convenient preparation of poly(ether amide)s in high yield at room temperature. Copyright © 2009 Society of Chemical Industry     

Shape memory property and underlying mechanism by the phase separation control of poly(ϵ‐caprolactone)/poly(ether‐b‐amide)

In this work, a poly(?‐caprolactone)/poly(ether‐b‐amide) blend with weight ratio 35/65 was prepared by solution mixing and compression molding. A simple and sensible method to control the phase separation structure was introduced by adjusting the temperature and time for the process of phase separation. Samples with obviously different morphology were obtained and the microstructure was studied by phase contrast optical microscopy, SEM and DSC. The shape memory properties were measured using dynamic mechanical analysis. The results show that the shape memory performance of the blend is closely related to the phase morphology, and the blend with co‐continuous structure has a better shape memory property. A model is put forward to illustrate schematically the microstructural evolution during the shape memory process. © 2018 Society of Chemical Industry     

Synthesis of unsaturated poly(ether amide)s based on amine‐terminated poly(ethylene glycol)

Novel water‐soluble unsaturated poly(ether amide)s (PEAs) were synthesized by low‐temperature polycondensation of fumaryl chloride and amine‐terminated poly(ethylene glycol) (Jeffamine®). The unsaturated copolymers were further chemically modified with thiols to provide reactive pendant functional groups. Hydrogels based on these copolymers were prepared by copolymerization of the PEA with N‐vinyl pyrrolidone exposure to ultraviolet (UV) irradiation. The resulting hydrogels exhibited a high swelling ratio, and the magnitude of swelling depended on the molecular weight of Jeffamine®. The swelling ratio and equilibrium water content tended to increase with increasing chain length of the Jeffamine® used in copolymer synthesis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 913–920, 1999     

Synthesis and characterization of poly(ether amide ether ketone)/poly(ether ketone ketone) copolymers

A new monomer, N,N′‐bis(4‐phenoxybenzoyl)‐m‐phenylenediamine (BPPD), was prepared by condensation of m‐phenylenediamine with 4‐phenoxybenzoyl chloride in N,N‐dimethylacetamide (DMAc). A series of novel poly(ether amide ether ketone) (PEAEK)/poly(ether ketone ketone) (PEKK) copolymers were synthesized by the electrophilic Friedel‐Crafts solution copolycondensation of terephthaloyl chloride (TPC) with a mixture of diphenyl ether (DPE) and BPPD, over a wide range of DPE/BPPD molar ratios, in the presence of anhydrous AlCl₃ and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The influence of reaction conditions on the preparation of copolymers was examined. The copolymers obtained were characterized by different physicochemical techniques. The copolymers with 10–25 mol % BPPD were semicrystalline and had remarkably increased T_gs over commercially available PEEK and PEKK due to the incorporation of amide linkages in the main chains. The copolymers III and IV with 20–25 mol % BPPD had not only high T_gs of 184–188°C, but also moderate T_ms of 323–344°C, having good potential for the melt processing. The copolymers III and IV had tensile strengths of 103.7–105.3 MPa, Young's moduli of 3.04–3.11 GPa, and elongations at break of 8–9% and exhibited outstanding thermal stability and good resistance to organic solvents. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Development of novel conducting composites of linseed‐oil‐based poly(urethane amide) with nanostructured poly(1‐naphthylamine)

Novel conducting polymer composites of linseed‐oil‐based poly(urethane amide) (LPUA) were synthesized using nanostructured poly(1‐naphthylamine) (PNA). The combination of the electrically conducting PNA with LPUA was accomplished through different weight percent loadings (0.5–2.5 wt%) of the conducting polymer. The particle size of the nanocomposite was determined using transmission electron microscopy and was found to be in the range 17–27 nm. Intermolecular hydrogen bonding between the two polymers and formation of urea linkages were confirmed by Fourier transform infrared spectroscopy. The electrical conductivity of the nanostructured conducting composites at 2.5 wt% loading was found to be comparable to that reported for polyaniline (PANI)/polyurethane at 30 wt% loading of PANI. This shows the superior properties of PNA and its potential for application in anti‐static as well as corrosion‐protective coatings. The present method of formulation of composites using an oil‐based polymer matrix is useful and economically feasible in the sense that a great variety of oil‐based polymer matrices can be used to form composites that are ecologically safe and exhibit properties similar to commercial polymers. Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of new biodegradable fluorescing poly(amide‐anhydrides)

Biodegradable/alternate/poly(amide‐anhydrides), [? C(O)PhNHC(O)(CH₂) _nC(O)O? ] _x, were synthesized by melt polycondensation, where n was 2, 3 or 4. The polymers have been characterized by NMR, DSC, wide‐angle X‐ray diffractometry and fluorometry. All the polymers are amorphous and their T_g ranges from 60 to 80 °C. Poly(p‐(carboxyethylformamido)benzoic anhydride) (PCEFB) as a film or in solution in chloroform can emit strong fluorescence, which was not observed for the other two polyanhydrides (n = 3, 4). The maximum emission wavelength varies with the excitation wavelength, 480 and 520 nm at the excitation wavelength of 470 nm, and 430 nm at 356 nm. In addition, the fluorescence intensities increase linearly with the molecular weight of PCEFB. Such inherent fluorescing properties of PCEFB, together with its biodegradability, make the polymer a potential visible matrix for drug delivery. © 2001 Society of Chemical Industry     

Blends of poly(ether imide) and an aromatic poly(ether amide): Phase behavior and CO2 transport properties

Blends of poly(ether imide) (PEI, Ultem 1000) and an aromatic poly(ether amide) were studied. Although homogeneous or heterogeneous blends can be obtained depending on the blend preparation method, the inherent miscibility of the mixture was finally established. The so-called enthalpy relaxation method was used to detect one or two glass transition temperatures in the blends in spite of the similarity of the pure component transitions. Fourier transform infrared analysis provided additional evidence of the specific interactions, which could be in the origin of the miscibility. A preliminary study of the influence of the homogeneity level in the transport properties of the blend films was also undertaken. Carbon dioxide at 1 bar was used as a penetrant. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2141–2149, 1998     

Synthesis of cardo containing asymmetric poly(ether‐naphthalimide‐phthalimide)s

A series of cardo based asymmetric polyimides containing bulky rigid naphthalimide and phthalimide groups were prepared from asymmetric monomer bishaloimide and bisphenols by solution polycondensation. Bishalo(naphthalimide‐phthalimide) monomers containing different terminal leaving groups (Cl, F, NO₂) were synthesized, and the reactivity difference of these monomers was compared for the successful synthesis of polyimides. The inherent viscosities of the polyimides were in the range 0.51 ? 0.60 dL g^?1 in N ‐methyl‐2‐pyrrolidone at 30 °C. These polyimides demonstrated good organosolubility and mechanical properties with tensile strengths of 93 ? 120 MPa, tensile moduli of 3.5 ? 5.3 GPa and elongations at break of 2.8% ? 4.3%. The polyimides showed high glass transition temperatures (T _g) ranging from 330 to 363 °C. The 10% weight loss (T _10%) of asymmetric polyimides reached 436 ? 500 °C in nitrogen and 417 ? 476 °C in air. The water uptake of the polyimides was in the range 0.35% ? 0.72%. © 2017 Society of Chemical Industry     

Synthesis and properties of new poly(amide‐imide)s based on 2,5‐bis(trimellitimido)chlorobenzene

A series of new aromatic poly(amide‐imide)s were synthesized by the triphenyl phosphite‐activated polycondensation of the diimide‐diacid, 2,5‐bis(trimellitimido)chlorobenzene (I) with various aromatic diamines in a medium consisting of N‐methyl‐2‐pyrrolidone (NMP), pyridine, and calcium chloride. The poly(amide‐imide)s had inherent viscosities of 0.76–1.42 dL g⁻¹. The diimide‐diacid monomer (I) was prepared from 2‐chloro‐p‐phenylenediamine with trimellitic anhydride. Most of the resulting polymers showed an amorphous nature and were readily soluble in a variety of organic solvents, including NMP and N,N‐dimethylacetamide. Transparent, flexible, and tough films of these polymers could be cast from N,N‐dimethylacetamide or NMP solutions. Their cast films had tensile strengths ranging from 74 to 95 MPa, elongations at break from 7 to 11%, and initial moduli from 1.38 to 3.25 GPa. The glass transition temperatures of these polymers were in the range of 233°–260°C, and the 10% weight loss temperatures were above 450°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1691–1701, 1999     

Synthesis,characterization, and properties of a linear poly(ester‐amide) containing ethylene glycol lactate sequences

A novel linear lactic acid‐based poly(ester‐amide) (LLPEA) was prepared via polyaddition of toluene‐2,4‐diisocyanate (TDI) with ethylene lactate succinic half‐ester diacid (ELDA), which contained ethylene glycol lactate sequences and derived from lactic acid. LLPEA was characterized with FTIR, GPC, DSC, TGA, and XRD. The weight average molecular weight and its polydisperse index of LLPEA could be 1.0 × 10⁵ and 2.0, respectively. DSC and XRD analysis showed that LLPEA was a semicrystalline polymer. The glass transition temperature, melting temperature, and the thermal decomposition temperature (50 wt %) of LLPEA were ?2, 94, and ～415°C, respectively. The contact angle determination indicated that LLPEA was a hydrophilic polymer. It was found that the yield strength, tensile strength, and elastic module of LLPEA could be 8.8, 9.6, and 176 MPa, respectively. In addition, the weight loss percentage of LLPEA was 2.5% after 157‐days immersion in activated sludge at ambient temperature, which suggested that LLPEA was degradable. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3805–3808, 2006     

Synthesis and properties of thio‐containing poly(ether ether ketone)s

A series of thio‐containing poly(ether ether ketone) (PEESK) polymers was synthesized by the introduction of thio groups from 4,4′ thiodiphenol (TDP) into the poly(ether ether ketone) (PEEK) structure via reaction between the phenol and aromatic fluoride groups. The effect of the thio groups on the properties of the PEESK materials was investigated. Differential scanning calorimetry (DSC) analysis and X‐ray diffraction (XRD) patterns show a depression in the crystallinity of the PEESKs with incorporation of the content of thio groups in the backbones. The crystalline structure was identified as an orthorhombic structure with lattice constants of a = 7.52 Å, b = 5.86 Å and c = 10.24 Å for all crystallizable PEESKs. The crystalline structures of the thio‐containing PEEK polymers were the same as that of the neat PEEK, which means the thio‐containing block in the whole thio‐containing PEEK molecule is almost excluded from the crystalline structure and the crystals are completely formed by ‘non‐thio’ blocks only. Due to the glass transition temperature (T_g) and melting temperature (T_m) depression with increase in the TDP content in the reaction system, the processability of the resultant thio‐containing PEEKs could be effectively improved. Copyright © 2004 Society of Chemical Industry     

Toughening of poly(propylene carbonate) by hyperbranched poly(ester‐amide) via hydrogen bonding interaction

Poly(propylene carbonate) (PPC) is a biodegradable alternative copolymer of propylene oxide and carbon dioxide. As an amorphous polymer with lower glass transition temperature around 35 °C, PPC shows poor mechanical performance in that it becomes brittle below 20 °C and its dimensional stability deteriorates above 40 °C; thus toughening of PPC is urgently needed. Here we describe a biodegradable hyperbranched poly(ester‐amide) (HBP) that is suitable for this purpose. Compared with pure PPC, the PPC/HBP blend with 2.5 wt% HBP loading showed a 51 °C increase in thermal decomposition temperature and a 100% increase in elongation at break, whilst the corresponding tensile strength remained as high as 45 MPa and tensile modulus showed no obvious decrease. Crazing as well as cavitation was observed in the scanning electron microscopy images of the blends, which provided good evidence for the toughening mechanism of PPC. The intermolecular hydrogen bonding interaction confirmed by Fourier transform infrared spectral analysis proved to be the reason for the toughening phenomenon. Copyright © 2011 Society of Chemical Industry     

Effects of poly(ethylene‐co‐propylene) elastomer on mechanical properties and combustion behaviour of flame retarded polyethylene/magnesium hydroxide composites

Magnesium hydroxide‐based halogen‐free flame retarded linear low density polyethylene composites containing poly(ethylene‐co‐propylene) elastomer were prepared in the melt process and subsequently vulcanized thermally. Influences of the elastomer on the mechanical properties, combustion characteristics and crystallization behaviour of polyethylene/magnesium hydroxide composites have been investigated. The results from the mechanical tests show that the incorporation of a suitable amount of elastomer into polyethylene/magnesium hydroxide composites after vulcanization can increase both the tensile strength and elongation greatly, compared with those of the composites without the elastomer. It has been found that the properties such as limiting oxygen index, UL‐94 rating, the time to ignition and the rate of heat release of polyethylene/magnesium hydroxide/elastomer composites are all improved in comparison with polyethylene/magnesium hydroxide composites at the same retardant level. Scanning electron microscopy studies show that the incorporation of the elastomer into polyethylene/magnesium hydroxide composites improves the compatibility between the filler and the polymer substrate. The degrees of crystallinity of polyethylene/magnesium hydroxide/elastomer composites decrease with increasing the elastomer content. © 2002 Society of Chemical Industry     

Synthesis,characterization and properties of biodegradable poly(butylene succinate)‐block‐poly(propylene glycol) segmented copolyesters

BACKGROUND: To obtain a biodegradable thermoplastic elastomer, a series of poly(ester‐ether)s based on poly(butylene succinate) (PBS) and poly(propylene glycol) (PPG), with various mass fractions and molecular weights of PPG, were synthesized through melt polycondensation. RESULTS: The copolyesters were characterized using ¹H NMR, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, mechanical testing and enzymatic degradation. The results indicated that poly(ester‐ether)s with high molecular weights were successfully synthesized. The composition of the copolyesters agreed very well with the feed ratio. With increasing content of the soft PPG segment, the glass transition temperature decreased gradually while the melting temperature, the crystallization temperature and the relative degree of crystallinity decreased. Mechanical testing demonstrated that the toughness of PBS was improved significantly. The elongation at break of the copolyesters was 2–5 times that of the original PBS. Most of the poly(ester‐ether) specimens were so flexible that they were not broken in Izod impact experiments. At the same time, the enzymatic degradation rate of PBS was enhanced. Also, the difference in molecular weight of PPG led to properties being changed to some extent among the copolyesters. CONCLUSION: The synthesized poly(ester‐ether)s having excellent flexibility and biodegradability extend the application of PBS into the areas where biodegradable thermoplastic elastomers are needed. Copyright © 2009 Society of Chemical Industry